高级氧化技术在水和废水处理中的应用2资料讲解.ppt

Click to edit Master title style,Click to edit Master text styles,Second level,Third level,Fourth level,Fifth level,*,高级氧化技术在水和废水处理中的应用,高级氧化处理,(AOPs),Advanced oxidation processes,(abbreviation:,AOPs,)refers to a set of chemical treatment procedures designed to remove organic and inorganic materials in,waste water,by,oxidation,.,Contaminants are oxidized by four different reagents:,ozone,hydrogen peroxide,oxygen,and air,in precise,pre-programmed dosages,sequences,and combinations.These procedures may also be combined with,UV,irradiation and specific catalysts.This results in the development of hydroxyl radicals.,The AOP procedure is particularly useful for cleaning biologically toxic or non-degradable materials such as,aromatics,pesticides,petroleum,constituents,and,volatile organic compounds,in waste water,1,.,(,来源,：,en.wikipedia.org/wiki/Advanced_oxidation_process,),高级氧化处理,(AOPs),Ruppert and Rupert(1994),have defined the AOP,s,as processes which involved the generation of hydroxyl radicals in sufficient quantity,such as O,3,/OH,-,O,3,/H,2,O,2,Fe,2+,/H,2,O,2,UVC/H,2,O,2,UVC/O,3,and UVA/TiO,2,.(,Ruppert G.,Rupert B.G.H.UV-O,3,UV-H,2,O,2,UV-TiO,2,and the photo-Fenton reaction comparison of advanced oxidation processes for wastewater treatment.,Chemosphere,1994,28,1447-1454.),高级氧化处理,(AOPs),高级氧化处理是,20,世纪,80,年代开始形成的处理有毒污染物技术，它的特点是通过反应产生羟基自由基，该自由基具有极强的氧化性，通过自由基反应能够将有机污染物有效地分解，甚至彻底地转化为无害无机物，如二氧化碳和水等。由于高级氧化工艺具有氧化性强、操作条件易于控制的优点，因此引起世界各国的重视，并相继开展了该方向的研究与开发工作。,（,来源：,环境工程中的高级氧化技术,）,高级氧化处理,(AOPs),Sulfate radical-based,AOPs,（,1,）,UV/S,2,O,8,2-,S,2,O,8,2-,+photons or heat,2SO,4,-,SO,4,-,+,OH,-,SO,4,2-,+,HO,SO,4,-,+,H,2,O,HSO,4,-,+,HO,（,2,）,Fe,2+,/S,2,O,8,2-,Ag,+,/,S,2,O,8,2-,Ag,+,+S,2,O,8,2-,Ag,2+,+SO,4,-,+SO,4,2-,Fe,2+,+,S,2,O,8,2-,Fe,3+,+,SO,4,2-,+SO,4,-,(3)Co,2+,/HSO,5,-,Fe,2+,/HSO5,-,Co,2+,+,HSO,5,-,Co,3+,+,SO,4,-,+,OH,-,Fe,2+,+,HSO,5,-,Fe,3+,+,SO,4,-,+,OH,-,高级氧化处理,(AOPs),(4)Granular Activated Carbon(GAC)/S,2,O,8,2-,GAC-OOH,+S,2,O,8,2-,SO,4,-,+GAC-OO,+,HSO,4,-,GAC-OOH,+S,2,O,8,2-,SO,4,-,+GAC-O,+,HSO,4,-,Table 1.Relative power of common oxidants,Compound,Oxidation potential(volts),Relative power of chlorine,Fluorine,3.06,2.25,Sulfate radical,(,SO,4,-,),2.5-3.10,1.84-2.28,Hydroxyl radical(HO),2.8,2.05,Atomic oxygen(O),2.42,1.78,Ferrate(VI),0.7-2.2,0.52-1.62,Ozone,2.08,1.52,Perhydroxyl radical,(HOO),1.70,1.25,Permanganate,1.67,1.23,Chlorine dioxide,1.50,1.10,Hypochlorous acid,1.49,1.10,Chlorine,1.36,1.0,Bromine,1.09,0.80,Hydrogen peroxide,0.87,0.64,Iodine,0.54,0.40,Oxygen,0.40,0.29,臭氧,(,Ozone,),Pale blue gas,slightly soluble in water,Sharp odor,Harmful effects on the respiratory systems of animals,Powerful oxidizing agent,臭氧技术在水处理中的应用,Removal of inorganic species such as ammonia nitrogen,(1),(2),in the presence of bromide,Removal of Fe,2+,and Mn,2+,Oxidation of natural organic matter like humic substances,(Humic substances are precursors of THMs and favor the regrowth in the network),臭氧技术在水处理中的应用,Increase in biodegradability,Oxidation of Persistent Organic Pollutants(POPs),Disinfection-more effective biocide than hydroxyl radicals(Can kill bacteria,virus and algae by reacting with cytoplasmic substances and degrading chromosomal deoxyribonucleic acid),Addition of 1,g/L O,3,leads to 99.99%reduction of,E.coli,in one minute.Ozonation has been widely used in the disinfection of drinking water in developed countries.,臭氧处理,(,Ozone,),Onsite generation(half-life in atmospheric conditions is half an hour,2O,3,3O,2,),Highly pH-dependent,(1)O,3,+OH,-,HO,2,-,+O,2,(2)HO,2,-,+O,3,O,3,-,+HO,2,(3)HO,2,H,+,+O,2,-,(4),O,2,-,+O,3,O,3,-,+O,2,(5)O,3,-,+H,+,HO,+O,2,臭氧处理,(,Ozone,),0.00,0.02,0.04,0.06,0.08,0.10,0.12,0.14,0.16,0.18,2,4,6,8,10,12,pHo,k(min,-1,),Fig.1b Peudo-first-order rate constant of 0.1mM linuron,（利谷隆）in,sole-O,3,system,at various pH levels(O,3,=1.71,10,-5,M),(,来源：,Rao Y.F.,Chu W.,Chemosphere,2009,74,1444-1449),Fig.1a Peudo-first-order rate constant of 0.2mM,C,arbofuran,(,克百威）in,sole-O,3,system,at various pH levels(O,3,=1.,8,10,-5,M),(,来源：,Lau T.K.,Chu W.,Graham N.,Water Sci.Tech,.2007,55,275-280.),臭氧处理,(,Ozone,),Highly selective,Table 2.Ozonation rate constants and OH rate constants for some organic compounds(,Legube B.and Leitner N.K.V.,Catalysis Today,1999,53,61-72,),Compounds,k,O3,(M,-1,s,-1,),k,OH,(M,-1,s,-1,),Benzene,20.4,7.8 10,9,Nitrobenzene,0.090.02,3.9 10,9,Toluene,14 3,3.0 10,9,Formic acid,5 5,1.310,8,Oxalic acid,410,-2,1.,4,10,6,Acetic acid,310,-5,1.,6,10,7,Succinic acid,310,-2,3.110,8,臭氧处理,(,Ozone,),Fig.2.Comparison of linuron decay(C/C,0,)and,TOC removal by the different treatment processes at pH 6(C,0,=0.1 mM),(,来源：,Rao Y.F.,Chu W.,Chemosphere,2009,74,1444-1449,),Highly selective Low mineralization,臭氧与其他技术联合处理,UV/O,3,O,3,/H,2,O,2,O,3,+,H,2,O,2,OH+,HO,2,-,+,O,2,(k,10,-2,M,-1,s,-1,),O,3,+,HO,2,-,OH+,2O,2,k=(5.5,1.0)10,6,M,-1,s,-1,),US/O,3,Heterogeneous catalytic ozonation such as AC(Activated Carbon)/O,3,MnO,2,/O,3,Al,2,O,3,/O,3,TiO,2,/O,3,Homogeneous catalytic ozonation,by metallic ions,Ozonation/electrolysis,UV/O,3,Direct Photolysis,Direct oxidation by ozone,Oxidation by hydroxyl radicals,(1)O,3,+H,2,O+,hv,H,2,O,2,+O,2,(2),H,2,O,2,+,hv,2,OH,UV/Ozone Reactor,Table 3 Design data for a 151 m,3,/day Ultrox plant,Reactor,Dimensions:L x W x H(m)2.5 x 4.9 x 1.5,Wet volume,(L)14,951,UV lamps:,Number of 65 watt lamps 378,Total power,(KW)25,Ozone generator,Dimensions:L x W x H(m)1.7 x 1.8 x 1.2,gms ozone/min 5.3,Kg ozone/d 7.7,Total power,(KW)7.0,Total energy required,(KW/day),768,Costs in the above table were considered to be competitive with activated carbon.,Typical design data for a 150 m,3,/d UV/ozone treatment process are shown,in the above table.The plant is designed to reduce a 50 ppm PCB,feed concentration to a 1 ppm effluent.,UV/Ozone Reactor Ultrox(Jones,1996),US/O,3,Pyrolysis,Oxidation by ozone,Oxidation by hydroxyl radicals,O,3,+,H,2,O,2,OH+,HO,2,-,+,O,2,(k,10,-2,M,-1,s,-1,),O,3,+,HO,2,-,OH+,2O,2,k=(5.5,1.0)10,6,M,-1,s,-1,),US/O,3,(,来源,:,He Z.Q.,Song S.,et al.,Chemosphere,2007,69,191-199)US/O,3,(,来源,:Ning B.,Graham N.J.,Lickiss P.D.,Water Environment Research,2007,79,2427-2436),.,Heterogeneous Catalytic Ozonation,AC(Activated Carbon)/Ozone,(1).Generation of free radicals:O,3,+AC,OH,(2).Generation of surace radicals:,O,3,+AC AC-O,AC-R+AC-O P,TiO,2,/Ozone,Ceramic honeycomb/Ozone,AC/Ozone,Fig.,3,.Evolution of the dimensionless concentration of oxalic acid at pH 3,(C,0,=1 mM,AC=0.5 g/L,Ctert-butanol=10 mM).,(,来源：,Faria,P.C.C.,Orfao,J.J.M.et al.,Applied catalysis B:Environmental,2008,79,237-243).,TiO,2,/Ozone,(,来源,:Beltran F.J.,Rivas F.J.,Espinosa R.M.,Applied Catalysis B:Environmental,2002,39,221-231),.,Ceramic honeycomb(2MgO2Al,2,O,3,-5SiO,2,)/Ozone,(,来源,:Zhao L.,Ma J.,Sun Z.Z.,Applied Catalysis B:Environmental,2008,79,244-253),.,Ceramic honeycomb/Ozone,(,来源,:Zhao L.,Ma J.,Sun Z.Z.,Applied Catalysis B:Environmental,2008,79,244-253),.,Homogeneous Catalytic Ozonation,by metallic ions,Reaction Mechanism,Fe,2+,+O,3,Fe,3+,+O,3,-,O,3,-,+H,+,HO,3,OH+O,2,Catalytic ozonation by metallic ions,O,3,alone Pb,2+,Cu,2+,Zn,2+,Fe,2+,Ti,2+,Mn,2+,(,来源,:Ni C.H.,Chen J.N.,Yang P.Y.,Water Science and Technolgoy,2002,47,77-82),.,Catalytic ozonation by Mn,2+,(,来源,:Ma J.,Graham,N.J.D.,Water Research,2000,34,3822-3828),.,Catalytic ozonation by Mn,2+,(,来源,:Xiao H.,Liu R.P.,et al.,Chemosphere,2008,72,1006-1012),.,Ozonation/electrolysis,Reaction Mechanism,O,3,+e O,3,-,at cathodes,O,3,-,+H,2,O,OH+O,2,+OH,-,Ozonation/electrolysis,(,来源,:Kishimoto N.,Morita Y.,et al.,Water Research,2005,39,4661-4672),.,Ozonation/electrolysis,(,来源,:Kishimoto N.,Morita Y.,et al.,Water Research,2005,39,4661-4672),.,Other Oxidation Technology,SO,4,-,-based,AOPs,UV/Persulfate(S,2,O,8,2-,),heat/S,2,O,8,2-,Fe,2+,/S,2,O,8,2-,Ag,+,/,S,2,O,8,2-,Co,2+,/,peroxymonosulfate(,HSO,5,-,),Fe,2+,/HSO,5,-,AC/Persulfate,Ferrate(VI),Permanganate,SO,4,-,-based,AOPs,(,来源,:Yang S.Y.,Wang P.,et al.,Journal of Hazardous Materials,2010,179,552-558),.,SO,4,-,-based,AOPs,(,来源,:Yang S.Y.,Wang P.,et al.,Journal of Hazardous Materials,2010,179,552-558),.,AC/Persulfate,(,来源,:Yang S.Y.,Yang X.,et al.,Journal of Hazardous Materials2011,186,659-666),.,Ferrate(VI),In,acidic,media:,FeO,4,2-,+8H,+,+3e,-,Fe,3+,+4H,2,O E,0,=2.2V,In,basic,media:,FeO,4,2-,+4H,2,O+3e,-,Fe(OH),3,+5OH,-,E,0,=0.7v,高铁酸盐在水处理中应用研究,Removal of cyanides(CN,-1,NCO,-,),Simultaneous removal of organic pollutants and phosphate,Elimination of sludge odor,Decolorization,Oxidation of POPs,Coagulation,Permanganate(MnO,4,-1,),In an,acidic,solution,permanganate(VII)is reduced to the colourless+2 oxidation state of the,manganese(II),(Mn,2+,)ion.,8 H,+,+MnO,4,+5 e,Mn,2+,+4 H,2,O,In a strongly,basic,solution,permanganate(VII)is reduced to the green+6 oxidation state of the,manganate,MnO,4,2,.,MnO,4,+e MnO,4,2,In a neutral medium,however,it gets reduced to the brown+4 oxidation state of,manganese dioxide,MnO,2,.,2 H,2,O+MnO,4,+3 e,MnO,2,+4 OH,+,S,trong,oxidizer,，,a,permanganate can oxidize an,amine,to a,nitro compound,2,3,an,alcohol,to a,ketone,4,an,aldehyde,to a,carboxylic acid,5,6,a terminal,alkene,to a,carboxylic acid,7,oxalic acid,to,carbon dioxide,8,and an,alkene,to a,diol,.,Permanganate(MnO,4,-1,),In alkene oxidations one intermediate is a cyclic Mn(V)species:,（来源：,en.wikipedia.org/wiki/Permanganate,）,高锰酸钾在水处理中的应用,强化预氯化消毒,(,减少了致癌物三卤甲烷的生成）,去除微量重金属离子例如,Mn,2+,，,As,3+,，,Pb,2+,Mn,2+,+2KMnO,4,+2H,2,O=5MnO,2,+2K,+,+4H,+,（中性和微酸性）,治理染料废水,去除难降解有机污染物,去除藻类（氧化降解微囊藻毒素,MC-LR,）,消毒,去除微量,Mn,2+,（三亚中法供水有限公司,-,水库）,（来源：王菊，潘孝楼，科技资讯，,2009,，,34,，,115-116.,）,难降解有机污染物的去除,（来源：,Hu,L.H.,Martin,H.M.et al.Environmental Science&Technology,2009,43,509-515.,）,Photocatalysis,1,、藤岛昭,(,光触媒之父）和本田健一,（,Fujishima,A.and Honda,K.Electrochemical Photolysis of Water at a Semiconductor Electrode.,Nature,1972,238(5358),37-38.,）,藤岛昭,TiO,2,-based Photocatalysis,光催化技术的应用研究,高速公路的隔音墙和街道路灯等装置上,汽车的喷涂材料,光催化剂公路（日本千叶县）,医学上消毒以及用来杀死癌细胞,保鲜水果,利用二氧化钛的亲水性制造不用擦拭的汽车后视镜等产品（东陶公司的渡部俊）,脱臭,染料电池,光催化制氢,*水处理（去除金属离子和难降解有机污染物）,贵重金属的回收（铂、金）,二氧化钛的载体,Activated Carbon(,活性炭,）,玻璃,铝片,硅胶,陶瓷,高分子聚合物,Modification of TiO,2,Composite Photocatalysts-TiO,2,/,CdS,TiO,2,/,Cu,2,O,TiO,2,/,Fe,2,O,3,TiO,2,/,WO,3,TiO,2,/,Bi,2,O,3,and so on.,Transition Metal Doping-,Fe,Cr,V,Co,Zr,etc.,Non-metal Doping-,N,C,P,S,etc.,Surface Sensitization-,Dye,polymer,Composite Photocatalysts,（来源：孙德智等，,环境工程中的高级氧化技术,，,p241),N-doped TiO,2,（来源：,Asahi,R.et al.,Science,2001,293,269-271,）,Wavelength,nm,Surface Sensitization,（来源：孙德智等，,环境工程中的高级氧化技术,，,p243),1.,染料容易吸附在半导体表面,2.,染料激发态（通常是单线态）的电位与半导体导带电位相匹配。,H,2,O,2,-Aided TiO,2,Photocatalysis under Visible Light,（来源：,Li,X.Z.,Chen,C.C.,Zhao,J.C.,Langmuir,200,1,17,4118-4122,.,),H,2,O,2,-Aided TiO,2,Photocatalysis under Visible Light,（来源：,Rao,Y.F.,Chu,W.,Environmental Science&Technology,2009,43,6183-6189.,),Figure 1.LNR degradation under different reaction conditions,H,2,O,2,-Aided TiO,2,Photocatalysis under Visible Light,Theory,1:,Titanium peroxide complex formed on the TiO,2,surface could extend the photoresponse of TiO,2,to the visible region and can be excited by visible light.The excited surface complex injects an electron to the conduction band of TiO,2,where the electrons on the conduction band of TiO,2,then,initiate the decomposition of H,2,O,2,to produce hydroxyl radicals(Li et al.2001).,H,2,O,2,-Aided TiO,2,Photocatalysis under Visible Light,（来源：,Li,X.Z.,Chen,C.C.,Zhao,J.C.,Langmuir,200,1,17,4118-4122,.,),1.Whether or not electron is generated in this system?,2.Whether or not hydroxyl radicals play a key role in the,degradation,of,organic compound in this system?,Photocatalytic Degradation Mechanism of LNR under Visible Light,Effect of radical scavengers,Effect of radical scavengers on visible-light photocatalysis of LNR,with the assistance of H,2,O,2,.,（来源：,Rao,Y.F.,Chu,W.,Environmental Science&Technology,2009,43,6183-6189.,),The Generation of Photocurrent,(a),(b),Visible-light-induced current(Iph)generation on a,TiO,2,/ITO electrode in water with or without H,2,O,2,（来源：,Rao,Y.F.,Chu,W.,Environmental Science&Technology,2009,43,6183-6189.,),Table 7-1:Identified degradation products and their main fragments determined by LC/ESI-MS,Compound,Retention time,Molecular weight,Molecular ion and main fragments,Structural formula,Detected in,UV Vis,1,8.96,186,185,165,141,119,2,9.49,278,277,250,233,217,119,3,10.02,262,261,156,119,109,4,10.65,200,199,42,137,119,5,12.62,200,199,137,119,6,13.90,230,229,37,119,109,7,14.61,264,263,176,119,109,8,14.83,250,249,219,202,176,137,119,109,9,15.44,15.56,220,219,203,176,137,119,109,Table 7-1:Identified degradation products and their main fragments determined by LC/ESI-MS,Contd,10,15.68,234,233,203,160,137,119,109,11,16.31,204,203,160,137,119,109,12,16.69,248,247,203,88,160,137,119,109,13,16.93,234,233,202,176,137,119,109,14,17.46,218,217,160,137,119,109,15,18.93,232,231,202,188 160,137,119.109,16 and 17,19.30,19.72,264,263,233,217,202,188,156,119,109,or,（来源：,Rao,Y.F.,Chu,W.,Environmental Science&Technology,2009,43,6183-6189.,),Photocatalytic Degradation Pathway of LNR under Visible Light or UV irradiation,（来源：,Rao,Y.F.,Chu,W.,Environmental Science&Technology,2009,43,6183-6189.,),Comparison between photocatalytic degradation of LNR under Visible Light and UV Irradiation,Comparison between the evolution profiles of generated intermediates in Vis/TiO,2/,H,2,O,2,and UV/TiO,2,system,(a).The evolution profiles of generated intermediates,in Vis/TiO,2,/H,2,O,2,;,(b).The evolution profiles of intermediates in UV/TiO,2,system.,（来源：,Rao,Y.F.,Chu,W.,Environmental Science&Technology,2009,43,6183-6189.,),Degradation Mechanism of LNR in TiO,2,/H,2,O,2,/Vis System,CB,VB,e,-,HOOTi,hv,(visible),H,2,O,2,HO,LNR,Intermediates,CO,2,H,2,O,NH,4,+,Cl,-,NO,3,-,Ti,HO,Scheme 7-1:Surface-Complex-Mediated Photodegradation of LNR in TiO,2,suspension with the existence of H,2,O,2,under Visible Irradiation,谢谢！,